Halogenobenzimidazoles and their use as microbicides

ABSTRACT

New halogenobenzimidazoles of the formula                    
     in which 
     A, R 1 , R 2 , R 3 , R 4  and X have the meanings given in the description, 
     and their acid addition salts and metal salt complexes, 
     a process for their preparation and their use as microbicides in crop protection and in the protection of materials. 
     New intermediates of the formulae                    
     in which 
     R 12 -R 17  and X have the meanings given in the description, 
     and processes for the preparation of these substances.

This application is a division of U.S. Ser. No. 09/636,720, filed onAug. 11, 2000, now U.S. Pat. No. 6,387,939, which is, in turn, adivision of U.S. Ser. No. 09/387,719, filed Aug. 25, 1999, now U.S. Pat.No. 6,160,001, issued on Dec. 12, 2000; which is, in turn, a division ofU.S. Ser. No. 09/011,250, filed Jan. 28, 1998, now U.S. Pat. No.6,020,354, issued Feb. 1, 2000, which is, in turn, a 371 ofPCT/EP96/03334, filed on Jul. 29, 1996.

The present invention relates to new halogenoben idazoles, to a processfor their preparation, and to their use as microbicides in cropprotection and in the protection of materials. The invention furthermorerelates to new intermediates and to a process for their preparation

It has already been disclosed that certain benzimidazole derivativeshave fungicidal properties (cf. DE-A 4 139 950 and EP-A 0 517 476).2-Cyano-3-dimethylaminosulphonyl-6,6,7,7-tetrafluoro-[1,4]dioxino[2,3-f]benzimidazoleand2-cyano-6,6-difluoro-2-methylaminosulphonyl-[1,3]dioxolo[4,5-f]benzidazole,for example, can be employed for controlling fungi. The efficacy ofthese substances is good, but leaves something to be desired in somecases when low rates of application are used.

There have now been found new halogenobenzimidazoles of the formula

in which

R¹, R², R³ and R⁴ independently of one another represent hydrogen,halogen, cyano, nitro, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy,alkylthio, halogenoalkylthio, alkylsulphinyl, halogenoalkylsulphinyl,alkylsulphonyl, halogenoalkylsulphonyl, optionally substitutedcycloalkyl, hydroxycarbonyl, alkylcarbonyl alkoxycarbonylcycloalkylcarbonyl, cycloalkoxycarbonyl or

R⁵ represents optionally substituted aryl or optionally substitutedheterocyclyl,

Z represents a direct bond, or represents —CH₂—, O, S, SO, SO₂, or CO,

or represents —CO—O—, the oxygen atom being bonded to R⁵,

or represents —SO₂—O—, the oxygen atom being bonded to R⁵,

or represents —S—CH₂—SO₂—, the sulphur atom of the thio group beingbonded to R⁵,

R⁶ and R⁷ independently of one another represent hydrogen, alkyl,halogenoalkyl, alkoxyalkyl, alkylcarbonyl, optionally substituted aryl,optionally substituted arylcarbonyl, optionally substitutedarylsulphonyl, optionally substituted arylaninocynyl or optionallysubstituted arylmethylsulphonyl, or

R⁶ and R⁷ together with the nitrogen atom to which they are bondedrepresent an optionally alkyl-substituted heterocyclic ring which canadditionally contain an oxygen atom or an alkylimino group and

Q represents a direct bond or a carbonyl group, or

R¹ and R², or R² and R³, or R³ and R⁴, in each case together, representan optionally substituted alkylene chain having 3 or 4 members in whichone or two (non-adjacent) carbon atoms can be replaced by oxygen atoms,

A represents one of the following groups —SO₂—R⁸, —CO—R⁹ or

Y represents oxygen or sulphur and

R⁸, R⁹, R¹⁰ and R¹¹ independently of one another represent alkyl,halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio,alkenyl, halogenoalkenyl, alkenyloxy, alkenylthio, alkenyl, alkinyloxyalkinylthio, amino, alkylamino, dialkylamino, optionally substitutedaryl, optionally substituted aryloxy, optionally substituted arylthio,optionally substituted cycloalkyl, optionally substituted cycloalkyloxy,optionally substituted cycloalkylthio, optionally substitutedcycloalkylamino, optionally substituted dicycloalkylamino or anoptionally substituted saturated or unsaturated heterocyclic radical, or

R¹⁰ and R¹¹ together with the phosphorus atom to which they are bondedrepresent an optionally substituted heterocyclic radical, and

X represents halogen,

and their acid addition salts and metal salt complexes.

Furthermore, it has been found that halogenobenzimidazoles of theformula (I) and their acid addition salts and metal salt complexes areobtained when

a) benzimidazole derivatives of the formula

in which

R¹, R², R³, R⁴ and X have the abovementioned meanings,

are reacted with halides of the formula

A-X¹  (III)

in which

A has the abovementioned meaning and

X¹ represents halogen,

if appropriate in the presence of an acid-binding agent and ifappropriate in the presence of a diluent,

and, if appropriate, the resulting compounds of the formula (I) aresubjected to an addition reaction with an acid or a metal salt.

Finally, it has been found that the halogenobenzimidazoles of theformula (I) and their acid addition salts and metal salt complexes havevery good microbicidal properties and can be employed both in cropprotection and in the protection of materials.

Surprisingly, the substances according to the invention display a betterfungicidal activity than2-cyano-3-dimethylaminosulphonyl-6,6,7,7-tetrafluoro-[1,4]-dioxino[2,3-f]benzimidazoleand2-cyano-6,6-difluoro-2-dimethylaminosulphonyl-[1,3]-dioxolo[4,5-f]benzimidazole,which are prior-art active compounds of similar constitution and thesame direction of action.

Formula (I) provides a general definition of the substances according tothe invention.

R¹, R², R³ and R⁴ independently of one another preferably representhydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro,straight-chain or branched alkyl having 1 to 8 carbon atoms,straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and1 to 13 identical or different halogen atoms, straight-chain or branchedalkoxy having 1 to 8 carbon atoms, straight-chain or branchedhalogenoalkoxy having 1 to 6 carbon atoms and 1 to 13 identical ordifferent halogen atoms, straight-chain or branched alkylthio having 1to 8 carbon atoms, straight-chain or branched halogenoalkylthio having 1to 6 carbon atoms and 1 to 13 identical or different halogen atoms,straight-chain or branched alkylsulphinyl having 1 to 8 carbon atoms,straight-chain or branched halogenoalkylsulphinyl having 1 to 6 carbonatoms and 1 to 13 identical or different halogen atoms, straight-chainor branched alkylsulphonyl having 1 to 8 carbon atoms, straight-chain orbranched halogenoalkylsulphonyl having 1 to 6 carbon atoms and 1 to 13identical or different halogen atoms, cycloalkyl having 3 to 6 carbonatoms which is optionally monosubstituted to pentasubstituted byidentical or different substituents from the series consisting ofhalogen and/or alkyl having 1 to 4 carbon atoms, or representhydroxycarbonyl, alkylcarbonyl having 1 to 6 carbon atoms in thestraight-chain or branched alkyl moiety, alkoxycarbonyl having 1 to 6carbon atoms in the straight-chain or branched alkoxy moiety,cycloalkylcarbonyl having 3 to 6 carbon atoms in the cycloalkyl moiety,cycloalkoxycarbonyl having 3 to 6 carbon atoms in the cycloalkyl moiety,or represent -Z-R⁵ or

R⁵ preferably represents aryl having 6 to 10 carbon atoms, it beingpossible for each of these radicals to be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of halogen, cyano, nitro, alkyl having 1 to 4 carbon atoms,alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms,halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1to 5 identical or different halogen atoms, halogenoalkylthio having 1 to4 carbon atoms and 1 to 5 identical or different halogen atoms,alkylsulphinyl having 1 to 4 carbon atoms, alkylsulphonyl having 1 to 4carbon atoms, halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to5 identical or different halogen atoms and/or halogenoalkylsulphonylhaving 1 to 4 carbon atoms and 1 to 5 identical or different halogenatoms.

R⁵ preferably also represents an unsaturated heterocyclyl radical having5 or 6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygenand/or sulphur, it being possible for these radicals to bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of halogen, alkyl having 1 to 4 carbon atoms,alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbonatoms and 1 to 5 identical or different halogen atoms, halogenoalkoxyhaving 1 to 4 carbon atoms and 1 to 5 identical or different halogenatoms, alkoxycarbonyl having 1 to 3 carbon atoms in the alkoxy moiety,cycloalkyl having 3 to 6 carbon atoms, cyano and/or nitro.

Z preferably also represents a direct bond, and —CH₂—, O, S, SO, SO₂ orCO,

or represents —CO—O—, the oxygen atom being bonded to R⁵,

or represents —SO₂—O—, the sulphur atom being bonded to R⁵,

or represents —S—CH₂—SO₂—, the sulphur atom of the thio group beingbonded to R⁵.

R⁶ and R⁷ independently of one another preferably represent hydrogen,straight-chain or branched alkyl having 1 to 6 carbon atoms,straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and1 to 13 identical or different halogen atoms, straight-chain or branchedalkoxyalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4carbon atoms in the alkyl moiety, alkylcarbonyl having 1 to 6 carbonatoms in the straight-chain or branched alkyl moiety, alkyl having 6 to10 carbon atoms, arylcarbonyl having 6 to 10 carbon atoms in the arylmoiety, arylsulphonyl having 6 to 10 carbon atoms, arylaninocynyl having6 to 10 carbon atoms in the aryl moiety, or arylmethylsulphonyl having 6to 10 carbon atoms in the aryl moiety, it being possible for each of theabovementioned aryl radicals to be monosubstituted to trisubstituted byidentical or different substituents from the series consisting ofhalogen, cyano, nitro, alkyl having 1 to 4 carbon atoms, alkoxy having 1to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkylhaving 1 to 4 carbon atoms and 1 to 5 identical or different halogenatoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkylthio having 1 to 4 carbon atomsand 1 to 5 identical or different halogen atoms, alkylsulphinyl having 1to 4 carbon atoms, alkylsulphonyl having 1 to 4 carbon atoms,halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5 identicalor different halogen atoms and/or halogenoalkylsulphonyl having 1 to 4carbon atoms and 1 to 5 identical or different halogen atoms.

R⁶ and R⁷ furthermore also together with the nitrogen atom to which theyare bonded preferably represent a heterocyclic ring having 5 or 6 ringmembers which can additionally contain an oxygen atom or aC₁-C₄-alkylimino group and which is optionally monosubstituted totrisubstituted by alkyl having 1 to 4 carbon atoms.

Q also preferably represents a direct bond or a carbonyl group.

R¹ and R², or R² and R³, or R³ and R⁴ in each case together alsopreferably represent an alkylene chain having 3 or 4 members in whichone or two (non-adjacent) carbon atoms can be replaced by oxygen atomsand which is optionally monosubstituted or hexasubstituted by halogen,alkyl having 1 to 4 carbon atoms and/or halogenoalkyl having 1 to 4carbon atoms and 1 to 9 halogen atoms.

X preferably represents fluorine, chlorine, bromine or iodine.

A also preferably represents one of the groups —SO₂—R⁸, —CO—R⁹ or

Y also preferably represents oxygen or sulphur.

R⁸, R⁹, R¹⁰ and R¹¹ independently of one another preferably representstraight-chain or branched alkyl having 1 to 4 carbon atoms,straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and1 to 5 identical or different halogen atoms, straight-chain or branchedalkoxy having 1 to 4 carbon atoms, straight-chain or branchedhalogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical ordifferent halogen, atoms, straight-chain or branched alkylthio having 1to 4 carbon atoms, straight-chain or branched halogenoalkylthio having 1to 4 carbon atoms and 1 to 5 identical or different halogen atoms,straight-chain or branched alkenyl having 2 to 4 carbon atoms,straight-chain or branched halogenoalkenyl having 2 to 4 carbon atomsand 1 to 5 identical or different halogen atoms, straight-chain orbranched alkenyloxy having 2 to 4 carbon atoms, straight-chain orbranched alkenylthio having 2 to 4 carbon atoms, straight-chain orbranched alkinyl having 2 to 4 carbon atoms, straight-chain or branchedalkinyloxy having 2 to 4 carbon atoms, straight-chain or branchedalkinylthio having 2 to 4 carbon atoms, amino, alkylamino having 1 to 4carbon atoms, dialkylamino having 1 to 4 carbon atoms in each alkylmoiety,

or represents phenyl, phenoxy or phenylthio, it being possible for eachof these radicals to be monosubstituted to trisubstituted by identicalor different substituents from the series consisting of fluorine,chlorine, bromine, nitro, alkyl having 1 to 4 carbon atoms,halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorineand/or bromine atoms, alkoxy having 1 to 4 carbon atoms and/orhalogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorineand/or bromine atoms,

or represents cycloalkyl having 3 to 7 carbon atoms, cycloalkyloxyhaving 3 to 7 carbon atoms, cycloalkylthio having 3 to 7 carbon atoms,cycloalkylamino having 3 to 7 carbon atoms, pyrrolidinyl, piperidinyl ormorpholinyl, it being possible for each of these abovementioned radicalsto be monosubstituted to trisubstituted by identical or differentsubstituents from the series consisting of fluorine, chlorine, bromine,alkyl having 1 to 4 carbon atoms and/or halogenoalkyl having 1 to 4carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms,

or represents an unsaturated heterocyclyl radical having 5 or 6 ringmembers and 1 to 3 heteroatoms, such as nitrogen, oxygen and/or sulphur,it being possible for these radicals to be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of halogen, cyano, nitro, hydroxyl, amino, formyl, carboxyl,carbamoyl, thiocarbamoyl, alkyl having 1 to 4 carbon atoms, alkoxyhaving 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 to4 carbon atoms and 1 to 5 identical or efferent halogen atoms,alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,cycloalkyl having 3 to 6 carbon atoms, halogenoalkylsulphinyl having 1to 4 carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylsulphonyl having 1 to 4 carbon atoms and 1 to 5 identicalor different halogen atoms, alkylamino having 1 to 4 carbon atoms,hydroxyalkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4carbon atoms in each alkyl group, alkylcarbonyl having 1 to 4 carbonatoms in the alkyl moiety, hydroximinoalkyl having 1 to 4 carbon atomsin the alkyl moiety, alkoximinoalkyl having 1 to 4 carbon atoms in thealkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety,alkylcarbonyloxy having 1 to 4 carbon atoms in the alkyl moiety and/orhalogenoalkylcarbonyloxy having 1 to 4 carbon atoms in the halogenoalkylgroup and 1 to 5 identical or different halogen atoms.

R¹⁰ and R¹¹ furthermore together with the phosphorus atom to which theyare bonded preferably represent a 5- or 6-membered heterocyclyl radicalwhich can contain one or two further heteroatoms, such as oxygen,sulphur and/or nitrogen, and which can be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of fluorine, chlorine, bromine, alkyl having 1 to 4 carbonatoms, alkoxy having 1 to 4 carbon atoms and/or halogenoalkoxy having 1to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms.

R¹, R², R³ and R⁴ independently of one another particularly preferablyrepresent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro,straight-chain or branched alkyl having 1 to 6 carbon atoms,halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorineand/or bromine atoms, straight-chain or branched alkoxy having 1 to 6carbon atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5fluorine, chlorine and/or bromine atoms, straight-chain or branchedalkylthio having 1 to 6 carbon atoms, halogenoalkylthio having 1 or 2carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms,straight-chain or branched alkylsulphinyl having 1 to 6 carbon atoms,halogenoalkysulphinyl having 1 or 2 carbon atoms and 1 to 5 fluorine,chlorine and/or bromine atoms, straight-chain or branched alkylsulphonylhaving 1 to 6 carbon atoms, halogenoalkylsulphonyl having 1 or 2 carbonatoms and 1 to 5 fluorine, chlorine and/or bromine atoms, cycloalkylhaving 3 to 6 carbon atoms which is optionally monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of fluorine, chlorine, bromine, methyl and/or ethyl, orrepresent hydroxycarbonyl, alkylcarbonyl having 1 to 4 carbon atoms inthe straight-chain or branched alkyl moiety, alkoxycarbonyl having 1 to4 carbon atoms in the straight-chain or branched alkoxy moiety,cycloalkylcarbonyl having 3 to 6 carbon atoms in the cycloalkyl moiety,cycloalkoxycarbonyl having 3 to 6 carbon atoms in the cycloalkyl moiety,or represent -Z-R⁵ or

R⁵ particularly preferably represents phenyl which can bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine, chlorine, bromine, cyano, nitro,methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, halogenoalkylhaving 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromineatoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine,chlorine and/or bromine atoms, halogenoalkylthio having 1 or 2 carbonatoms and 1 to 5 fluorine, chlorine and/or bromine atoms,methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl,halogenoalkylsulphinyl having 1 or 2 carbon atoms and 1 to 5 fluorine,chlorine and/or bromine atoms and/or halogenoalkylsulphonyl having 1 or2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms.

R⁵ also particularly preferably represents an unsaturated heterocyclylradical having 5 or 6 ring members and 1 to 3 heteroatoms, such asnitrogen, oxygen and/or sulphur, it being possible for each of theseradicals to be monosubstituted or disubstituted by identical ordifferent substituents from the series consisting of fluorine, chlorine,bromine, methyl, ethyl, methoxy, ethoxy, halogenoalkyl having 1 or 2carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms,halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorineand/or bromine atoms, methoxycarbonyl, ethoxycarbonyl, cycloalkyl having3 to 6 carbon atoms, cyano and/or nitro.

Z also particularly preferably represents a direct bond, and alsorepresents CH₂, O, S, SO, SO₂ or CO,

or represents —CO—O—, the oxygen atom being bonded to R⁵,

or represents —SO₂—O, the sulphur atom being bonded to R⁵,

or represents —S—CH₂—SO—, the sulphur atom of the thio group beingbonded to R⁵.

R⁶ and R⁷ independently of one another particularly preferably representhydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms,halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorineand/or bromine atoms, straight-chain or branched alkoxyalkyl having 1 to3 carbon atoms in the alkoxy moiety and 1 to 3 carbon atoms in the alkylmoiety, alkylcarbonyl having 1 to 4 carbon atoms in the straight-chainor branched alkyl moiety, phenyl, phenylcarbonyl, phenylsulphonyl,phenylaminocarbonyl or phenylmethylsulphonyl, it being possible for eachof the abovementioned phenyl radicals to be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of fluorine, chlorine, bromine, cyano, nitro, alkyl having 1or 2 carbon atoms, alkoxy having 1 or 2 carbon atoms, alkylthio having 1or 2 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5fluorine, chlorine and/or bromine atoms, halogenoalkoxy having 1 or 2carbon atoms and 1 to fluorine, chlorine and/or bromine atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 fluorine,chlorine and/or bromine atoms, alkylsulphinyl having 1 or 2 carbonatoms, alkylsulphonyl having 1 or 2 carbon atoms, halogenoalkylsulphinylhaving 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromineatoms and/or halogenoalkylsulphonyl having 1 or 2 carbon atoms and 1 to5 fluorine, chlorine and/or bromine atoms.

R⁶ and R⁷ furthermore also together with the nitrogen atom to which theyare bonded particularly preferably represent a sated heterocyclic ringhaving 5 or 6 ring members which is optionally monosubstituted totrisubstituted by methyl and/or ethyl, it being possible for a carbonatom of the ring to be replaced by oxygen or methylimino.

Q also particularly preferably represents a direct bond or a carbonylgroup.

R¹ and R², or R² and R³, or R³ and R⁴, in each case together alsoparticularly preferably represent an alkylene chain having 3 or 4members which is optionally monosubstituted to trisubstituted byfluorine, chlorine, methyl and/or trifluoromethyl and in which one ortwo (non-adjacent) carbon atoms can be replaced by oxygen.

X also particularly preferably represents fluorine, chlorine, bromine oriodine.

A also particularly preferably represents one of the groups

—SO₂—R⁸, —CO—R⁹ or

Y also particularly preferably represents oxygen or sulphur.

R⁸, R⁹, R¹⁰ and R¹¹ independently of one another particularly preferablyrepresent methyl, ethyl, n- or i-propyl, n, i-, s- or t-butyl,trifluoromethyl, trifluoroethyl, methoxy, ethoxy, n- or i-propoxy, n-,i-, s- or t-butoxy, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, methylthio, ethylthio, n- ori-propylthio, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, alkyl, n- or s-butenyl; alkyloxy, n- ors-butenyloxy; allylthio, n- or s-butenylthio; propargyl, n- ors-butinyl; propargyloxy; propargylthio; amino; methylamino, ethylamino,n- or i-propylamino, n-, i-, s- or t-butylamino; dimethylamino,diethylamino, di-n- or i-propylamino, methylethylamino, methyl-n- ori-propylamino;

or represent phenyl, phenoxy or phenylthio, it being possible for eachof these radicals to be monosubstituted to trisubstituted by identicalor different substituents from the series consisting of fluorine,chlorine, bromine, nitro, methyl, ethyl, n- or i-propyl, methoxy,ethoxy, n- or i-propoxy, trifluoromethyl and/or trifluoromethoxy;

or represent cyclopropyl, cyclopentyl, cyclohexyl, cyclopropyloxy,cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclopentylthio,cyclohexylthio, cyclopropylamino, cyclopentylamino, cyclohexylamino,1-pyrrolidinyl, 1-piperidinyl, and 1-morpholinyl, it being possible foreach of these radicals to be monosubstituted to trisubstituted byidentical or different substituents from the series consisting offluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl and/ortrifluoromethyl,

or represents an unsaturated heterocyclyl radical having 5 or 6 ringmembers and 1 to 3 heteroatoms, such as nitrogen, oxygen and/or sulphur,it being possible for each of these radicals to be monosubstituted ordisubstituted by identical or different substituents from the seriesconsisting of fluorine, chlorine, bromine, cyano, nitro, hydroxyl,amino, formyl, carboxyl, carbamoyl, thiocarbamoyl, alkyl having 1 to 4carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms,halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorineand/or bromine atoms, alkoxycarbonyl having 1 or 2 carbon atoms in thealkoxy moiety, cycloalkyl having 3 to 6 carbon atoms,halogenoalklsulphinyl having 1 or 2 carbon atoms and 1 to 5 fluorine,chlorine and/or bromine atoms, halogenoalkylsulphonyl having 1 or 2carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms,alkylamino having 1 or 2 carbon atoms, hydroxyalkylamino having 1 or 2carbon atoms, dialkylamino having 1 or 2 carbon atoms in each alkylgroup, alkylcarbonyl having 1 or 2 carbon atoms in the alkyl moiety,hydroximinoalkyl having 1 or 2 carbon atoms in the alkyl moiety,alkoximinoalkyl having 1 or 2 carbon atoms in the alkoxy moiety and 1 or2 carbon atoms in the alkyl moiety, alkylcarbonyloxy having 1 or 2carbon atoms in the alkyl group and/or halogenoalkylcarbonyloxy having 1or 2 carbon atoms in the halogenoalkyl group and 1 to 5 fluorine,chlorine and/or bromine atoms.

R¹⁰ and R¹¹ furthermore together with the phosphorus atom to which theyare bonded particularly preferably represent a 5- or 6-memberedheterocyclyl radical which can contain one or two filter heteroatoms,such as oxygen, sulphur and/or nitrogen, and which can bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of methyl, ethyl, n- or i-propyl, methoxy,ethoxy, n- or i-propoxy, chlorine and/or trifluoromethyl.

R¹, R², R³ and R⁴ independently of one another very particularlypreferably represent hydrogen, fluorine, chlorine, bromine, cyano,nitro, or represent methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- ori-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl,ethylsulphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy,difluoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl,tifluoromethylsulphonyl, acetyl, acetyloxy, methoxycarbonyl,ethoxycarbonyl, cyclopropyl, cyclohexyl, or represent Z-R⁵ or

R⁵ very particularly preferably represents phenyl which can bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of fluorine, chlorine, bromine, cyano, nitro,or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- ori-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl,ethylsulphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy,difluoromethylthio, trifluoromethylthio, difluoromethylsulphinyl and/ortrifluoromethylsulphonyl.

R⁵ also very particularly preferably represents pyrrolyl, furyl,thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl,isoxazolyl, oxadiazolyl, thiadiazolyl, 1,2,3-triazinyl, 1,2,4-triazinyl,1,3,5-triazinyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl, itbeing possible for each of these radicals to be monosubstituted ordisubstituted by identical or different substituents from the seriesconsisting of fluorine, chlorine, methyl, methoxy, trifluoromethyl,trifluoromethoxy and/or trifluoroethoxy.

Z also very particularly preferably represents a direct bond, orrepresents CH₂, O, S, SO, SO₂, CO,

or represents —CO—O—, the oxygen atom being bonded to R⁵,

or represents —SO₂—O—, the sulphur atom being bonded to R⁵,

or represents —S—CH₂—SO₂—, the sulphur atom of the thio group beingbonded to R⁵.

R⁶ and R⁷ independently of one another very particularly preferablyrepresent hydrogen methyl, ethyl, n-propyl, isopropyl or phenyl.

R⁶ and R⁷ furthermore also together with the nitrogen atom to which theyare bonded very particularly preferably represent pyrrolidinyl,piperidinyl, morpholinyl or 4-methylpiperazinyl.

Q also very particularly preferably represents a direct bond or acarbonyl group.

R¹ and R², or R² and R³, or R³ and R⁴, in each case together, also veryparticularly preferably represent the groups —CF₂—O—CF₂—, —O—CF₂—O—,—O—CF₂—CHF—O—, —O—CHF—CHF—O—, —O—CF₂—CF₂—CFCl—O— or —O—CFCl—CFCl—O—.

X also very particularly preferably represents fluorine, chlorine,bromine or iodine.

A also very particularly preferably represents one of the groups

—SO₂—R⁸, —CO—R⁹ or

Y also very particularly preferably represents oxygen or sulphur.

R⁸, R⁹, R¹⁰ and R¹¹ independently of one another particularly preferablyrepresent methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,trifluoromethyl, trifluoroethyl, methoxy, ethoxy, n- or i-propoxy, n-,i-, s- or t-butoxy, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, methylthio, ethylthio, n- ori-propylthio, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, alkyl, n- or s-butenyl; allyloxy, n- ors-butenyloxy; alkylthio, n- or s-butenylthio; propargyl, n- ors-butinyl; propargyloxy; propargylthio; amino; methylamino, ethylamino,n- or i-propylamino, n-, i-, s- or t-butylamino; dimethylamino,diethylamino, di-n- or i-propylamino, methylethylamino, methyl-n- ori-propylamino;

or represent phenyl, phenoxy or phenylthio, it being possible for eachof these radicals to be monosubstituted to trisubstituted by identicalor different substituents from the series consisting of fluorine,chlorine, bromine, nitro, methyl, ethyl, n- or i-propyl, methoxy,ethoxy, n- or i-propoxy, trifluoromethyl and/or trifluoromethoxy;

or represent cyclopropyl, cyclopentyl, cyclohexyl, cyclopropyloxy,cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclopentylthio,cyclohexylthio, cyclopropylamino, cyclopentylamino, cyclohexylamino,1-pyrrolidinyl, 1-piperidinyl, and 1-morpholinyl, it being possible foreach of these radicals to be monosubstituted to trisubstituted byidentical or different substituents from the series consisting offluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl and/ortrifluoromethyl, or

represent pyrrolyl, furyl, thienyl, pyrazolyl, imidazolyl, thiazolyl,isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl,1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, pyridinyl,pyrimidinyl, pyrazinyl or pyridazinyl, it being possible for each ofthese radicals to be monosubstituted or disubstituted by identical ordifferent substituents from the series consisting of fluorine, chlorine,bromine, cyano, nitro, amino, hydroxyl, formyl, carboxyl, carbamoyl,thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- ori-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl,ethylsulphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy,difluoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl, methylamino, ethylamino, n- or i-propylamino,dimethylamino, diethylamino, acetyl, propionyl, acetyloxy,methoxycarbonyl, ethoxycarbonyl, methylsulphonyloxy, ethylsulphonyloxy,hydroxyiminomethyl, hydroxyiminoethyl, methoxyiminomethyl,ethoxyiminomethyl, methoxyiminoethyl and/or ethoxyiminoethyl.

R¹⁰ and R¹¹ furthermore also together with the phosphorus atom to whichthey are bonded very particularly preferably represent a 5- or6-membered heterocyclyl radical which can contain one or two furtherheteroatoms, such as oxygen, sulphur and/or nitrogen, and which can bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of methyl, ethyl, n- or i-propyl, methoxy,ethoxy, n- or i-propoxy, chlorine and/or trifluoromethyl.

The definitions of radicals given above, in general or in preferredranges, apply to the end products of the formula (I) and, analogously,to the starting materials or intermediates required in each case for thepreparation.

Other preferred compounds according to the invention are additionproducts of acids and those halogenobenzimidazoles of the formula (I) inwhich R¹, R², R³, R⁴, A and X have those meanings which have beenmentioned as being preferred for these radicals.

The acids which can be subjected to the addition reaction preferablyinclude hydrohalic acids, such as, for example, hydrochloric acid andhydrobromic acid, in particular hydrochloric acid, furthermorephosphoric acid, sulphuric acid, nitric acid, mono- and bifunctionalcarboxylic acid and hydroxycarboxylic acids, such as, for example,acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid,citric acid, salicylic acid, sorbic acid and lactic acid, and alsosulphonic acids, such as, for example, p-toluenesulphonic acid,1,5-naphthalenedisulphonic acid, saccharine and thiosaccharine.

Other preferred compounds according to the invention are additionproducts of salts of metals of main groups II to IV and sub-groups I andII and also IV to VIII of the Periodic Table of the Elements and thosehalogenobenzimidazoles of the formula (I) in which R¹, R², R³, R⁴, A andX have those meanings which have been mentioned as being preferred forthese radicals.

Particularly preferred in this context are salts of copper, zinc,manganese, magnesium, tin, iron and of nickel. Suitable anions of thesesalts are those which are derived from those acids which lead tophysiologically acceptable addition products. Particularly preferredacids of his type are, in this context, the hydrohalic acids, such as,for example, hydrochloric acid and hydrobromic acid, furthermorephosphoric acid, nitric acid and sulphuric acid.

Examples of substances according to the invention which may be mentionedare the halogenobenzimidazoles listed in the tables which follow:

TABLE 1

where A represents the following substituents:

H₃C—SO₂— H₅C₂—SO₂—

TABLE 2 (Ib)

where A represents the substituents mentioned in Table 1.

TABLE 3 (Ic)

where A represents the substituents mentioned in Table 1.

TABLE 4 (Id)

where A represents the substituents mentioned in Table 1.

TABLE 5 (Ie)

where A represents the substituents mentioned in Table 1.

TABLE 6 (If)

where A represents the substituents mentioned in Table 1.

TABLE 7 (Ig)

where A represents the substituents mentioned in Table 1.

TABLE 8 (Ih)

where A represents the substituents mentioned in Table 1.

TABLE 9 (Ii)

where A represents the substituents mentioned in Table 1.

TABLE 10 (Ij)

where A represents the substituents mentioned in Table 1.

TABLE 11 (Ik)

where A represents the substituents mentioned in Table 1.

TABLE 12 (Il)

where A represents the substituents mentioned in Table 1.

TABLE 13 (Im)

where A represents the substituents mentioned in Table 1.

TABLE 14 (In)

where A represents the substituents mentioned in Table 1.

TABLE 15 (Io)

where A represents the substituents mentioned in Table 1.

TABLE 16 (Ip)

where A represents the substituents mentioned in Table 1.

If 2-chloro-1H-benzimidazole and toluene-4-sulphonyl chloride are usedas starting substances, the course of process a) according to theinvention can be illustrated by the following equation:

Formula (II) provides a general definition of the benzimidazolederivatives required as starting substances for carrying out process (a)according to the invention. In this formula (II), R¹, R², R³, R⁴ and Xpreferably, or in particular, have those meanings which have alreadybeen mentioned in connection with the description of the compounds ofthe formula (I) according to the invention as being preferred, orparticularly preferred, for R¹, R², R³, R⁴ and X.

Some of the benzimidazole derivatives of the formula (II) are known(compare Chem. Pharm. Bull. 1981, 29, 2403; Synthesis 1988, 767; J.Chem. Soc. 1922, 947; WO-A 9408456; WO-A 9207867 Bull. Soc. Chim. Fr.1988, 1, 139-142; EP-A 308918; J. C. S. Chem. Com. 1976, 430; LiebigsAnn. Chem. 1961, 649, 114 and J. Prakt. Chem. 1965, 28, 297).

The benzimidazole derivatives of the formula

in which

R¹², R¹³, R¹⁴ and R¹⁵ independently of one another represent hydrogen,halogenoalkoxy or halogenoalkylthio, at least one of the radicalsmentioned representing halogenoalkoxy or halogenoalkylthio, or

R¹² and R¹³, or R¹³ and R¹⁴, or R¹⁴ and R¹⁵, in each case together withthe carbon atoms to which they are bonded orm a five- or six-memberedheterocyclic ring which has one or two (non-adjacent) oxygen atoms andwhich is at least monosubstituted by halogen and

X represents halogen,

are new.

Benzimidazole derivatives of the formula (IIa) can be prepared by

(b) reacting benzimidazoles of the formula

in which

R¹², R¹³, R¹⁴ and R¹⁵ have the abovementioned meanings

with halogenating agents, if appropriate in the presence of a diluentand if appropriate in the presence of an acid-binding agent, or

c) reacting bromobenzimidazoles of the formula

in which

R¹², R¹³, R¹⁴ and R¹⁵ have the abovementioned meanings

with hydrofluoric, hydrochloric or hydriodic acid or with a salt of theformula

M⁺X²⁻  (V)

in which

M represents a metal equivalent or a quaternary ammonium sulphoniumsulphoxonium or phosphonium ion and

X² represents fluorine, chlorine or iodine,

if appropriate in the presence of a diluent.

Formula (IIa) provides a general definition of the new benzimidazolederivatives.

R¹², R¹³, R¹⁴ and R¹⁵ independently of one another preferably representhydrogen, straight-chain or branched halogenoalkoxy having 1 to 6 carbonatoms and 1 to 13 identical or different halogen atoms, straight-chainor branched halogenoalkylthio having 1 to 6 carbon atoms and 1 to 13identical or different halogen atoms, at least one of the radicalsmentioned representing halogenoalkoxy or halogenoalkylthio.

R¹² and R¹³, or R¹³ and R¹⁴, or R¹⁴ and R¹⁵, in each case together withthe carbon atoms to which they are bonded, also preferably represent afive- or six-membered heterocyclic ring having one or two (non-adjacent)oxygen atoms which is monosubstituted to tetrasubstituted by halogen.

X preferably represents fluorine, chlorine, bromine or iodine.

R¹², R¹³, R¹⁴ and R¹⁵ independently of one another particularlypreferably represent hydrogen, difluromethoxy, trifluoromethoxy,difluorochloromethoxy, difluorobromomethoxy, trifluoroethoxy,difluoromethylthio, trifluoromethylthio, difluorochloromethyltio ordifluorobromomethyltio, at least one of the radicals being other thanhydrogen.

R¹² and R¹³, or R¹³ and R¹⁴, or R¹⁴ and R¹⁵, in each case together withthe carbon atoms to which they are bonded, also particularly preferablyform a five- or six-membered, heterocyclic ring having one or two(non-adjacent) oxygen atoms which is monosubstituted to tetrasubstitutedby fluorine, chlorine and/or bromine.

X also particularly preferably represents fluorine, chlorine, bromine oriodine.

If 5-trifluoromethoxy-1H-benzimidazole and N-bromosuccinimide are usedas starting substances, the course of process (b) according to theinvention can be illustrated by the following equation:

Formula (IV) provides a general definition of the benzimidazolesrequired as starting substances for carrying out process (b) accordingto the invention. In this formula, R¹², R¹³, R¹⁴ and R¹⁵ preferably, orin particular, have those meanings which have already been given inconnection with the description of the compounds of the formula (IIa) asbeing preferred, or particularly preferred, for R¹², R¹³, R¹⁴ and R¹⁵.

Some of the benzimidazoles of the formula (IV) are known.5-Pentafluoroethoxy-1H-benzimidazole, for example, has already beendescribed (cf. Biomed. Environ. Mass Spectrom. (1989), 18(10), 872-877).

The benzimidazoles of the formula

in which

R¹² represents hydrogen, halogenoalkoxy or halogenoalkylthio,

R¹⁵ represents hydrogen, halogenoalkoxy or halogenoalkylthio,

R¹⁶ represents hydrogen, halogenoalkylthio or halogenoalkoxy, with theexception of pentafluoroethoxy,

R¹⁷ represents hydrogen, halogenoalkylthio or halogenoalkoxy, with theexception of pentafluoroethoxy,

but where at least one of the radicals R¹², R¹⁵, R¹⁶ and R¹⁷ is otherthan hydrogen, or

R¹² and R¹⁶, or R¹⁶ and R¹⁷, or R¹⁷ and R¹⁵, in each case together withthe carbon atoms to which they are bonded, form a five- or six-memberedheterocyclic ring having one or 2 (non-adjacent) oxygen atoms which isat least monosubstituted by halogen

are new.

The benzimidazoles of the formula (IVa) can be prepared by

d) reacting phenylenediamines of the formula

in which

R¹², R¹⁵, R¹⁶ and R¹⁷ have the abovementioned meanings

with formic acid, with one of its salts, or with one of its derivatives,such as, for example, formamide, trimethyl orthoformate,dialkylformamide acetate, formamide, s-triazine or carbon monoxide, at atemperature of from 0° C. to 180° C., preferably from 20° C. to 150° C.,if appropriate in the presence of a diluent, such as, for example,water, methanol, ethanol or methoxyethanol.

Formula (IV-a) provides a general definition of the new benzimidazoles.

R¹² preferably represents hydrogen, straight-chain or branchedhalogenoalkoxy having 1 to 6 carbon atoms and 1 to 13 identical ordifferent halogen atoms, or represents straight-chain or branchedhalogenoalkylthio having 1 to 6 carbon atoms and 1 to 13 identical ordifferent halogen atoms.

R¹⁵ preferably represents hydrogen, straight-chain or branchedhalogenoalkoxy having 1 to 6 carbon atoms and 1 to 13 identical ordifferent halogen atoms, or represents straight-chain or branchedhalogenoalkylthio having 1 to 6 carbon atoms and 1 to 13 identical ordifferent halogen atoms.

R¹⁶ preferably represents hydrogen, straight-chain or branchedhalogenoalkylthio having 1 to 6 carbon atoms and 1 to 13 identical ordifferent halogen atoms, or represents straight-chain or branchedhalogenoalkoxy having 1 to 6 carbon atoms and 1 to 13 identical ordifferent halogen atoms, but with the exception of pentafluoroethoxy.

R¹⁷ preferably represents hydrogen, straight-chain or branchedhalogenoalkoxy having 1 to 6 carbon atoms and 1 to 13 identical ordifferent halogen atoms, or represents straight-chain or branchedhalogenoalkoxy having 1 to 6 carbon atoms and 1 to 13 identical ordifferent halogen atoms, but with the exception of pentafluoroethoxy.

However, one of the radicals R¹², R¹⁵, R¹⁶ and R¹⁷ must be other thanhydrogen.

R¹² and R¹⁶, or R¹⁶ and R¹⁷, or R¹⁷ and R¹⁵, can, in each case, togetherwith the carbon atoms to which they are bonded, also preferably form afive- or six-membered heterocyclic ring having one or two (non-adjacent)oxygen atoms which is monosubstituted to tetrasubstituted by halogen.

R¹², R¹⁵, R¹⁶ and R¹⁷ independently of one another particularlypreferably represent hydrogen difluoromethoxy, trifluoromethoxy,difluoromethoxy, difluorobromomethoxy, trifluoroethoxy,difluoromethylthio, trifluoromethylthio, difluoromethylthio ordifluorobromomethylthio, at least one of the radicals being other thanhydrogen.

R¹² and R¹⁶, or R¹⁶ and R¹⁷, or R¹⁷ and R¹⁵, in each case together withthe carbon atoms to which they are bonded, also particularly preferablyform a five- or six-membered heterocyclic ring having one or two(non-adjacent) oxygen atoms which is monosubstituted to tetrasubstitutedby fluorine, chlorine and/or bromine.

If 4-trifluoromethoxy-o-phenylenediamine and formic acid are used asstarting substances, the course of process (d) according to theinvention can be illustrated by the following equation:

Formula (VI) provides a general definition of the phenylenediaminesrequired as starting substances for carrying out process (d) accordingto the invention. In this formula (VI), R¹², R¹⁵, R¹⁶ and R¹⁷preferably, or in particular, have those meanings which have alreadybeen mentioned in connection with the description of the compounds ofthe formula (IVa) as being preferred, or particularly preferred, forR¹², R¹⁵, R¹⁶ and R¹⁷.

The phenylenediamines of the formula (VI) are known; their preparationis described, for example, in DE-A 3 605 977, DE-A 3 621 215 or DE-A 4237 564.

When carrying out process (b) according to the invention, suitablehalogenating agents are, preferably, elemental halogen orN-halogenoimides, such as N-bromo-succinimide or N-chloro-succinimide.

Diluents which are suitable for carrying out process (b) according tothe invention are all customary inert organic solvents. The followingcan preferably be used: aliphatic, alicyclic or aromatic hydrocarbonssuch as petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; furthermorehalogenated hydrocarbons, such as chlorobenzene, dichlorobenzene,dichloromethane, chloroform tetrachloromethane, dichloroethane ortrichloroethane; moreover ethers, such as diethyl ether, diisopropylether, methyl t-butyl ether, methyl t-amyl ether, dioxane,tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole;furthermore nitriles, such as acetonitrile, propionitrile, n- ori-butyronitrile or benzonitrile, or else amides, such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,N-methylpyrrolidone and hexamethylphosphoric triamide.

Suitable acid-binding agents for carrying out process (b) according tothe invention are all customary inorganic and organic acid acceptors.The following can preferably be used: the hydrides, hydroxides, amides,alcoholates, acetates, carbonates or hydrogen carbonates of alkalineearth metals or alkali metals, such as sodium hydride, sodium amide,sodium methylate, sodium ethylate, potassium tert-butylate, sodiumhydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate,potassium acetate, calcium acetate, sodium carbonate, potassiumcarbonate, potassium hydrogen carbonate, furthermore ammonium acetate orammonium carbonate, or tertiary amines, such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out process (b) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at tempt between −20° C. and +120° C., preferablybetween 0° C. and 80° C.

When carrying out process (b) according to the invention and also whencarrying out the other processes according to the invention, thereactions are generally carried out under atmospheric pressure. However,it is also possible to carry out the reactions under elevated pressureor, in the event that no gaseous components are employed, under reducedpressure.

When carrying out process (b) according to the invention an equivalentamount, or else an excess, of halogenating agent is generally employedper mole of benzimidazole of the formula (IV). Working-up is carried outby customary methods.

If 2-bromo-5-trifluoromethoxy-1H-benzimidazole and sodium chloride areused as starting substances, the course of process (c) according to theinvention can be illustrated by the following equation:

Formula (IIb) provides a general definition of the bromobenzimidazolesrequired for carrying out process (c) according to the invention. Inthis formula (IIb), R¹², R¹³, R¹⁴ and R¹⁵ preferably, or in particular,have those meanings which have already been mentioned in connection withthe description of the compounds of the formula (IIa) according to theinvention as being preferred, or particularly preferred, for R¹², R¹³,R¹⁴ and R¹⁵.

The compounds of the formula (IIb) are intermediates according to theinvention and can be prepared by process (b) according to the invention.

Hydrofluoric acid, hydrochloric acid or hydriodic acid, furthermorerequired for carrying out process (c) according to the invention aregenerally known chemicals for synthesis.

Formula (V) provides a general definition of the salts alternativelyalso required as reactants for carrying out process (c) according to theinvention. In this formula, M preferably represents an alkali metal, inparticular lithium, sodium or potassium, or a quaternary ammonium,sulphonium, sulphoxonium or phosphonium ion, preferably thealkylammonium, having in each case 1 to 12 carbon atoms in theindividual alkyl chains, and X² represents fluorine, chlorine or iodine.

The salts of the formula (V) are known chemicals for synthesis.

Suitable diluents for carrying out process (c) according to theinvention are all customary inert organic solvents. The following canpreferably be used: aliphatic, alicyclic or aromatic hydrocarbons suchas petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane,benzene, toluene, xylene or decalin; furthermore halogenatedhydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane,chloroform, tetrachloromethane, dichloroethane or trichloroethane;furthermore ethers, such as diethyl ether, diisopropyl ether, methylt-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran,1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; moreover ketones,such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; inaddition nitriles, such as acetonitrile, propionitrile, n- ori-butyronitrile or benzonitrile; furthermore amides, such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide; and also esters,such as methyl acetate or ethyl acetate, and sulphoxides, such asdimethyl sulphoxide, and sulphones, such as sulpholane. If appropriate,the reaction can also be carried out in a two-phase system, for examplein a mixture of toluene and water.

When carrying out process c) according to the invention, the reactiontemperatures can, again, be varied within a substantial range. Ingeneral, the process is carried out at temperatures between −20° C. and+150° C., preferably between 0° C. and 120° C.

When carrying out process (c) according to the invention, an equivalentamount, or else an excess, of the reactant in question is generallyemployed per mole of bromo-benzimidaole. Working-up is carried out bycustomary methods.

Formula (III) provides a general definition of the halides furthermorerequired as reactants for carrying out process (a) according to theinvention. In this formula (III), A preferably, or in particular, hasthe meaning which has already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred or particularly preferred, for A. X¹preferably represents chlorine or bromine.

The halides of the formula (III) are known and/or can be prepared byknown processes (J. Heterocyclic Chem. 1981, 997-1006).

Suitable diluents for carrying out process (a) according to theinvention are all inert organic solvents. The following can preferablybe used: aliphatic, alicyclic or aromatic hydrocarbons, such aspetroleum ether, hexane, heptane, cyclohexane, methylcyclohexane,benzene, toluene, xylene or decalin; halogenated hydrocarbons, such aschlorobenzene, dichlorobenzene, dichloromethane, chloroform,tetrachloromethane, dichlorobenzene, or trichloroethane; ethers, such asdiethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amylether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethaneor anisole; ketones, such as acetone, butanone, methyl isobutyl ketoneor cyclohexanone; nitriles, such as acetonitrile, propionitrile, n- ori-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide; esters, such as methyl acetate or ethylacetate, sulphoxides, such as dimethyl sulphoxide, and sulphones, suchas sulpholane.

If appropriate, process (a) according to the invention is carried out inthe presence of a suitable acid acceptor. Suitable acid acceptors areall customary inorganic or organic bases. The following can preferablybe used: the hydrides, hydroxides, amides, alcoholates, acetates,carbonates or hydrogen carbonates of alkaline earth metals or alkalimetals, such as sodium hydride, sodium amide, sodium methylate, sodiumethylate, potassium tert-butylate, sodium hydroxide, potassiumhydroxide, sodium acetate, potassium acetate, calcium acetate, sodiumcarbonate, potassium carbonate, potassium hydrogen carbonate or sodiumhydrogen carbonate, furthermore ammonium hydroxide, ammonium acetate orammonium carbonate, and also tertiary amines, such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out process (a) according to the invention, the reactiontemperature can be varied within a substantial range. In general, theprocess is carried out at temper between 0° C. and 150° C., preferablybetween 20° C. and 120° C.

To carry out process (a) according to the invention, 1 to 15 mol,preferably 1 to 2 mol, in particular 1 to 1.3 mol, of halide of theformula (III) are generally employed per mole of benzimidazolederivative of the formula (II).

Process (a) according to the invention is generally carried out underatmospheric pressure. However, it is also possible to carry out theprocess under elevated or reduced pressure, in general between 0.1 barand 10 bar.

Working-up is carried out by customary methods.

The halogenobenzimidazoles of the formula (I) can be converted into acidaddition salts or metal salt complexes.

Suitable acids for preparing acid addition salts of the compounds of theformula (I) are preferably those which have already been mentioned aspreferred acids in connection with the description of the acid additionsalts according to the invention.

The acid addition salts of the compounds of the formula (I) can beobtained in a simple manner by customary salt formation methods, forexample by dissolving a compound of the formula (I) in a suitable inertsolvent and adding the acid, for example hydrochloric acid, and isolatedin a known manner, for example by filtration, and, if appropriate,purified by washing with an inert organic solvent.

Suitable salts for the preparation of metal salt complexes of thecompounds of the formula (I) are preferably those salts of metals whichhave already been mentioned as being preferred metal salts in connectionwith the description of the metal salt complexes according to theinvention.

The metal salt complexes of the compounds of the formula (I) can beobtained in a simple manner by customary methods, for example bydissolving the metal salt in alcohol, for example ethanol, and addingthe solution to compounds of the formula (I). Metal salt complexes canbe isolated in a known manner, for example by filtration, and, ifappropriate, purified by recrystallization.

The active compounds according to the invention have a potentmicrobicidal activity and can be employed in practice for controllingundesirable microorganisms. The active compounds are suitable for use ascrop protection agents, in particular as fungicides in crop protectionand also in the protection of materials.

Fungicidal agents are employed in crop protection for controllingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericidal agents are employed in crop protection for controllingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Some pathogens causing fungal and bacterial diseases which come underthe generic names listed above may be mentioned as examples, but not byway of limitation:

Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv.lachrynans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae,

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea (conidia form: Drechslera, syn: Helminthosporium);

Cocliobolus species, such as, for example, Cochiobolus sativus (conidiaform: Drechslera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae andPseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The fact that the active compounds are well tolerated by plants at theconcentrations required for controlling plant diseases permits thetreatment of aerial parts of plants, of propagation stock and seeds, andof the soil.

The active compounds according to the invention can be employedparticularly successfully for controlling diseases in fruit andvegetable growing and viticulture, such as, for example, againstPhytophthora or Plasmopara species, or for controlling rice diseases,such as, for example, against the pathogen causing rice blast disease(Pyricularia oryze).

In the protection of materials, the substances according to theinvention can be employed for protecting industrial materials againstinfection with and destuction by, undesired microorganisms.

Industrial materials in the present context are understood as meaningnon-live materials which have been prepared for use in industry. Forexample, industrial materials which are intended to be protected byactive compounds according to the invention from microbial change ordestruction can be glues, sizes, paper and board, textiles, leather,wood, paints and plastic articles, cooling lubricants and othermaterials which can be infected with, or destroyed by, microorganisms.Parts of production plants, for example cooling-water circuits, whichmay be impaired by the multiplication of microorganisms may also bementioned within the scope of the materials to be protected. Industrialmaterials which may be mentioned within the scope of the presentinvention are preferably glues, sizes, papers and boards, leather, wood,paints, cooling lubricants and heat-transfer liquids.

Microorganisms, capable of bringing about degradation of, or change in,the industrial materials, which may be mentioned are, for example,bacteria, fungi, yeasts, algae and slime organisms. The active compoundsor agents according to the invention preferably act against fungi, inparticular moulds, and against slime organisms and algae.

Microorganisms of the following genera may be mentioned as examples:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa and

Staphylococcus, such as Staphylococcus aureus.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted to the customary formulations, such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols and microencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurfactants, that is emulsifiers and/or dispersants, and/or foamformers. In the case of the use of water as an extender, organicsolvents can, for example, also be used as auxiliary solvents. Thefollowing are mainly suitable as liquid solvents: aromatics such asxylene, toluene or alkylnaphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons such ascyclohexane or paraffins, for example mineral oil fractions, alcoholssuch as butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulphoxide, or else water, liquefied gaseous extenders or carriers areto be understood as meaning liquids which are gaseous at ambienttemperature and under atmospheric pressure, for example aerosolpropellants such as halogenated hydrocarbons, or else butane, propane,nitrogen and carbon dioxide; suitable solid carriers are: for exampleground natural minerals such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals such as highly disperse silica, alumina and silicates; suitablesolid carriers for granules are: for example crushed and fractionatednatural rocks such as calcite, marble, pumice, sepiolite and dolomite,or else synthetic granules of inorganic and organic meals, and granulesof organic material such as sawdust, coconut shells, maize cobs andtobacco stalks; suitable emulsifiers and/or foam formers are: forexample non ionic and anionic emulsifiers, such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates,or else protein hydrolysates; suitable dispersants are: for examplelignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colourants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The activity and the spectrum of action of the active compounds can beincreased by adding, if appropriate, other antimicrobially activecompounds, fungicides, bactericides, herbicides, insecticides or otheractive compounds for widening the spectrum of action or achievingspecific effects, such as, for example, an additional protection againstinsects. These mixtures may have a wider spectrum of action than thecompounds according to the invention.

In many cases, synergistic effects are achieved, i.e. the activity ofthe mixture exceeds the activity of the individual components. Examplesof particularly advantageous co-components in mixtures are the followingcompounds:

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide;8-hydroxyquinoline sulphate; methyl(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate;methyl (E)-methoximio[alpha(o-tolyloxy)-o-tolyl]-acetate; 2-phenylphenol(OPP), aldimorph, ampropylfos, anilazine, azaconazole,

benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate,

calcium polysulphide, captafol, captan, carbendazim, carboxin,quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate,cufraneb, cymoxanil, cyproconazole, cyprofuran,

dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran,diethofencarb, difenoconazole, dimethirimol, dimethomorpl, diniconazole,dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine,drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole,

fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole,flusilazole, flusulfamide, flutolanil, flutriafol, folpet,fosetyl-aluminum, fthalide, fuberidazole, furalaxyl, furmecyclox,

guazatine,

hexachlorobenzene, hexaconazole, hymexazol,

imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione,isoprothiolane,

kasugamycin, copper preparations such as: copper hydroxide, coppernaphthenate, copper oxychloride, copper sulphate, copper oxide,oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb,mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb,methfuroxam, metiram, metsulfovax, myclobutanil,

nickel dimethyldithiocarbamate, nitroal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxycarboxin,

pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin,polyoxin, probenazole, prochloraz, procymidone, propamocarb,propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil,pyroquilon,

quintozene (PCNB),

sulphur and sulphur preparations,

tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid,triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole,tridemorph, triflurizole, triforine, triticonazole,

validamycin A, vinclozolin,

zineb, ziram

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations

Insecticides/Acaricides/Nematicides:

abamectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin,amitraz avermectin, AZ 60541, azadirachtin, azinphos A, azinphos Mazocyclotin,

Bacillus thuringiensis,4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile,bendiocarb, bensultap, betacyfluthrin, bifenthrin, BPMC, brofenprox,bromophos A, bufencarb, buprofezin, butocarboxim, butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,chloethocarb, chlorethoxyfos, chlorfenvinphos, chorfluazuron,chlormephos,N-[(6-chloro-3-pyridinyl)methyl]-N′-cyano-N-methyl-ethanimidazmide,chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine,cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyromazine,

deltamethrin, demeton M, demeton S, demeton S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,

edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, fluazuron, flucycloxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos,formothion, fosthiazate, fubfenprox, furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion,ivermectin,

lambda-cyhalothrin, lufenuron,

malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos,methamidophos, methidathion, methiocarb, methomyl, metolcarb,milbemectin, monocrotophos, moxidectin,

naled, NC 184, nitenpyram,

omethoate, oxamyl, oxydemethon M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamidon, phoxim, primicarb, pirimiphos M, pirimiphos A,profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate,pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum,pyridaben, pyrimidifen, pyriproxifen,

quinalphos,

salithion, sebufos, silafluofen, sulfotep, sulprofos,

tebufenozid, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin,temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb,thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin,triarathen, triazophos, triazuron, trichlorfon, triflumuron,trimethacarb,

vamidothion, XMC, xylylcarb, zetamethrin.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators is also possible.

The active compound combinations preferably comprise 0.1 to 99.9%, inparticular 1 to 75%, particularly preferably 5 to 50%, of the activecompound, the remainder to 100% being made up by one or more of theabovementioned co-components.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. They are used in the customary manner, for example bypouring, spraying, atomizing, spreading, dusting, foaming, brushing onand the like. It is furthermore possible to apply the active compoundsby the ultra-low volume method or to inject the active compoundformulation, or the active compound itself into the soil. The seed ofthe plants can also be treated.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001% by weight.

In the treatment of seed, amounts of active compound of from 0.001 to 50g, preferably 0.01 to 10 g, are generally required per kilogram of seed.

In the treatment of the soil, active compound concentrations of from0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight,are required at the site of action.

The compositions used for the protection of industrial materialsgenerally comprise an amount of 1 to 95%, preferably 10 to 75%, of theactive compounds.

The use concentrations of the active compounds according to theinvention depend on the species and the occurrence of the microorganismsto be controlled and on the composition of the material to be protected.The optimal rate of application can be determined by test series. Ingeneral, the use concentrations are in the range of from 0.001 to 5% byweight, preferably 0.05 to 1.0% by weight, based on the material to beprotected.

The preparation and use of active compounds according to the inventionare illustrated by the examples which follow.

PREPARATION EXAMPLES Example 1

Process (a)

0.2 g (5 mmol) of sodium hydride (60%) is added at room temperature to astirred mixture of 1.4 g (5 mmol) of2-bromo-6,6-difluoro-[1,3]dioxolo[4,5-f]benzimidazole and 30 ml ofabsolute tetrahydrofuran, and the reaction mixture is then stirred for30 minutes at room temperature. 1.0 g (5.5 mmol) of3,5-dimethylisoxazole-4-sulphonyl chloride is then added, and themixture is stirred for a further 3 hours at room temperature. Forworking-up, the reaction mixture is poured into 100 ml of water. Theresulting mixture is extracted twice using in each case 50 ml of ethylacetate. The combined organic phases are dried over sodium sulphate andconcentrated under reduced pressure. The residue which remains ischromatographed on silica gel using methylene chloride as the eluent.This gives 1.2 g (75% of theory) of1-(3,5-dimethylisoxazole-4-sulphonyl)-2-bromo-6,6-difluoro[1,3]-dioxolo-[4,5-f]-benzimidazolein the form of a colourless solid of melting point 130-134° C.

Preparation of Precursors

Process (b) 2.0 g (10 mmol) of6,6-difluoro[1,3]dioxolo[4,5-f]benzimidazole are added to a suspensionof 0.48 g (12 mmol) of 60% sodium hydride in 20 ml of absolutedimethylformamide, the mixture is stirred for 30 minutes at 20° C., 2.2g (12 mmol) of N-bromosuccinimide are then added, and the mixture isstirred for a further 30 minutes at the same temperature. The mixture ispoured onto 250 g of ice, brought to pH=4 using glacial acetic acid andextracted three times using in each case 100 ml of ethyl acetate. Thecombined organic extracts are dried over sodium sulphate andconcentrated in vacuo. The residue which remains is stirred with 50 mlof water, and the resulting residue is filtered off and dried.

This gives 2.3 g (83% of theory) of2-bromo-6,6-difluoro[1,3]dioxolo[4,5-f]benzimidazole as a white solid ofa melting range of 160 to 164° C.

Process (d)

80 ml of 98% strength formic acid are added to 37.6 g (0.2 mol) of5,6-diamino-2,2-difluorobenzodioxole, and the mixture is refluxed for 4hours. After cooling, the mixture is rendered alkaline using 2N sodiumhydroxide solution. The precipitate is filtered off, washed using 200 mlof water and dried.

This gives 38.1 g (95% of theory) of6,6-difluoro[1,3]dioxolo[4,5-f]benzimidazole in the form of a solid.

The substances listed in the table which follows are also prepared bythe methods given above.

TABLE 17

Ex. Physical No. R¹ R² R³ R⁴ A X constant  2 H —O—CF₂—CF₂—O— H

Br m.p.: 90° C. (Decomp.)  3 H —O—CF₂—CF₂—O— H

Br m.p.: 115- 119° C.  4 H —O—CF₂—O— H

Br m.p.: 112- 115° C.  5 H H

H

Cl m.p.: 48-53° C.  6 H —O—CF₂—O— H

Br m.p.: 117- 124° C.  7 H —O—CF₂—O— H

Br ¹H NMR*) (DMSO): 1.37-1.56 (m, 6H): 2.97-3.40 (m, 4H); 7.75(s, ¹H);7.98 (s, 1H)  8 H —O—CF₂—O— H

Br m.p.: 181- 185° C.  9 H —O—CF₂—O— H

Br m.p.: 180- 183° C. 10 H —O—CF₂—O— H

Br m.p.: 85- 90° C. 11 H —O—CF₂—O— H

Br m.p.: 133- 136° C. 12 H —O—CF₂—O— H

Br m.p.: 132- 136 13 H —O—CF₂—O— H

Br m.p.: 53- 58° C. 14 H —O—CF₂—O— H

Br m.p.: 94- 97° C. 15 H —O—CF₂—O— H H₃C—SO₂— Br m.p.: 170- 173° C. 16 H—O—CF₂—O— H H₅C₂—SO₂— Br m.p.: 97- 101° C. 17 H —O—CF₂—CF₂—O— H

Br m.p.: 170- 174° C. 18 H —O—CF₂—CF₂—O— H

Br m.p.: 153- 156° C. 19 H —O—CH₃ H H

Cl m.p.: 105- 108° C. 20 H —O—CF₂—O— H

Br m.p.: 162- 164° C. 21 H —OCH₃ H H

—Cl m.p.: 127-130° C. 22 H H

H

—Cl m.p.: 80- 84° C. 23 H H H H

—Cl m.p.: 181-183° C. 24 H H

H

—Cl m.p.: 97-104° C. 25 H H

H

—Cl NMR: 2.28 26 H —O—CF₂—O— H

—Cl m.p.: 129-131° C. 27 H —Cl —Cl H

—Br m.p.: 185- 190° C. 28 H —O—CF₂—CF₂—O— H

—Br m.p.: 180-184° C. 29 H —O—CF₂—CF₂—O— H —SO₂—CH₃ —Br m.p.: 170- 174°C. 30 H —O—CF₂—O— H

—Br m.p.: 170- 174° C. 31 H H H H

—Cl m.p.: 200° C. 32 H H

H

—Cl m.p.: 135-138° C. 33 H —O—CF₂—CF₂—O— H

—Cl m.p.: 130- 136° C. 34 H —O—CF₂—O— H

—Br m.p.: 219- 223° C. 35 H H

H

Cl m.p.: 170-173° C. *) The ¹H NMR spectra were recorded inhexa-deuterodimethyl sulphoxide (DMSO-D₆) using tetramethylsilane (TMS)as the internal standard. The value given is the chemical shift, δ, inppm.

Example 36

Process (c)

Hydrogen chloride gas is passed for 2 hours at 120° C. into a solutionof 2.8 g (10 mmol) of2-bromo-6,6-difluoro[1,3]dioxolo[4,5-f]benzimidazole in 30 ml ofdimethylformamide. The mixture is poured onto 200 g of ice/water andextracted three times using in each case 80 ml of ethyl acetate. Thecombined organic extracts are dried over sodium sulphate andconcentrated under reduced pressure. The residue is chromatographed onsilica gel using diethyl ether. This gives 0.5 g (21.5% of theory) of2-chloro-6,6-difluoro[1,3]dioxolo[4,5-f]benzimidazole as a white solidof melting point >220° C.

Example 37

2-Bromo-6,6,7,7-tetrafluoro[1,4]dioxino[2,3-f]benzimidazole is alsoprepared by the method described in Example 1.

Melting point: 170-174° C.

Example 38

2-Chloro[1,4]dioxino[2,4-f]benzimidazole is also prepared by the methoddescribed in Example 1.

Melting point: 150° C.

Example 39

6,6,7,7-Tetrafluoro[1,4]dioxino[2,3-f]benzimidazole is also prepared bythe method described in Example 1.

Melting point: 70-74° C.

USE EXAMPLES Example A

Phytophthora Test (Tomato)/Protective

Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weightof alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew moist. After the spray coatinghas dried on, the plants are inoculated with an aqueous spore suspensionof Phytophthora infestans.

The plants remain in an incubation cabin at 100% relative atmospherichumidity and approx. 20° C.

The test is evaluated 3 days after inoculation. 0% means an efficacywhich corresponds to the control while an efficacy of 100% means that nodisease is observed.

Active compounds, active compound concentrations and test results can beseen from the table which follows.

TABLE A Phytophthora test (tomato)/protective) Efficacy in % based onthe untreated control at an active Active compound compoundconcentration of 50 ppm According to the invention:

99

97

86

94

94

97

96

95

99

99

99

97

97

95

Example B

Plasmopara Test (Vines)/Protective

Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weightof alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are inoculated with an aqueous spore suspensionof Plasmopara viticola and then remain in a humid chamber at 20 to 22°C. and 100% relative atmospheric humidity for 1 day. The plants are thenplaced in a greenhouse at 21° C. and about 90% atmospheric humidity for5 days. The plants are then moistened and placed in a humid chamber for1 day.

The test is evaluated 6 days after inoculation. 0% means an efficacywhich corresponds to the control while an efficacy of 100% means that nodisease is observed

Active compounds, active compound concentrations and test results can beseen from the table which follows.

TABLE B Plasmopara test (vines)/protective Efficacy in % based on theuntreated control at an active compound Active compounds concentrationof 50 ppm According to the invention:

99

93

92

99

100

100

96

Example C

Venturia Test (Apple)/Protective

Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weightof alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are inoculated with an aqueous conidiasuspension of the pathogen causing apple scab (Venturia inaequalis) andthen remain in an incubation cabin at 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

The test is evaluated 12 days after inoculation. 0 or means an efficacywhich corresponds to the control while an efficacy of 100% means that nodisease is observed.

Active compounds, active compound concentrations and test results can beseen from the table which follows.

TABLE C Venturia test (apple)/protective Efficacy in % based on theuntreated control at an active compound con- Active compound centrationof 100 ppm According to the invention:

89

What is claimed is:
 1. A halogenobenzimidazole of the formula:

in which R¹, R², R³ and R⁴ independently of one another representhydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro,straight-chain or branched alkyl having 1 to 8 carbon atoms,straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and1 to 13 identical or different halogen atoms, straight-chain or branchedalkoxy having 1 to 8 carbon atoms, straight-chain or branchedhalogenoalkoxy having 1 to 6 carbon atoms and 1 to 13 identical ordifferent halogen atoms, straight-chain or branched alkylthio having 1to 8 carbon atoms, straight-chain or branched halogenoalkylthio having 1to 6 carbon atoms and 1 to 13 identical or different halogen atoms, orrepresent -Z-R⁵, R⁵ represents aryl having 6 to 10 carbon atoms, itbeing possible for aryl to be monosubstituted to trisubstituted byidentical or different substituents selected from the group consistingof halogen, cyano, nitro, alkyl having 1 to 4 carbon atoms, alkoxyhaving 1 to 4 atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkylhaving 1 to 4 carbon atoms and 1 to 5 identical or different halogenatoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkylthio having 1 or 4 carbon atomsatoms 1 to 5 identical or different halogen atoms, alkylsulphinyl having1 to 4 carbon atoms, alkylsulphonyl having 1 to 4 carbon atoms,halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5 identicalor different halogen atoms and halogenoalkylsulphonyl having 1 to 4carbon atoms and 1 to 5 identical or different halogen atoms, Zrepresents O or S, X represents fluorine, chlorine, bromine or iodine,and A represents the group —SO₂—R⁸, wherein R⁸ denotes 1-pyrrolidinvl,it being possible for the 1-pyrrolidinyl to be monosubstituted totrisubstituted by identical or different substitutents selected from thegroup consisting of fluorine, chlorine, bromine, methyl, ethyl, n-ori-propyl and/or trifluoromethyl, or an acid addition salt or metal saltcomplex thereof.
 2. A microbicidal composition comprising amicrobicidally effective amount of a halogenobenzimidazole according toclaim 1 or an acid addition salt or metal salt complex thereof and aninert diluent.
 3. A method for the control of undesired microorganismscomprising applying an effective amount therefor of ahalogenobenzimidazole according to claim 1 or an acid addition salt ormetal sale complex thereof to the microorganisms or to their habitat orto an area from which it is desired to exclude such microorganisms. 4.The halogenobenzimidazole according to claim 1, which has the formula:


5. A method for the control of undesired microorganisms comprisingapplying an effective amount therefor of a halogenobenzimidazoleaccording to claim 4 or an acid addition salt or metal salt complexthereof to the microorganisms or to their habitat or to an area fromwhich it is desired to exclude such microorganisms.